Method of manufacturing capacitor having ferroelectric film for nonvolatile memory cell

ABSTRACT

A capacitor in a ferroelectric nonvolatile memory (FERAM) comprising a lower electrode formed on a semiconductor substrate; a ferroelectric thin film formed on the lower electrode; an upper electrode formed on the ferroelectric thin film; a first protective layer consisting of one or more layers formed between the semiconductor substrate and the lower electrode, and composed of a material selected from those of Group IVa transition metal, Group Va transition metal, Group IVa transition metal nitride, Group Va transition metal nitride, silicon nitride, nickel and palladium; and a second protective layer consisting of one or more layers formed on the upper electrode, and composed of a material selected from those of Group IVa transition metal, Group Va transition metal, Group IVa transition metal nitride, Group Va transition metal nitride, nickel and palladium. Since the ferroelectric capacitor is enclosed with composite films of such materials, it becomes possible to prevent diffusion of hydrogen and intrusion of water content therein to consequently avert deterioration of the characteristics.

This is a division, of application Ser. No. 08/722.640, filed Sep. 27,1996 pending.

BACKGROUND OF THE INVENTION

The present invention relates to a nonvolatile memory cell having acapacitor formed by the use of a ferroelectric film, and also to amethod of manufacturing the same.

With recent progress of the film forming technology, rapid studies arecurrently advanced in the application of nonvolatile memory cells eachusing a ferroelectric thin film. In the nonvolatile memory cell, it ispossible to perform fast polarization inversion of a ferroelectric thinfilm and also fast rewriting effected by utilizing the residualpolarization of the thin film. The nonvolatile memory cells withferroelectric thin films being currently studied are broadly classifiedinto a type to detect a change of a stored charge amount in a dielectriccapacitor, and a type to detect a resistance change caused byspontaneous polarization of a ferroelectric. The semiconductor memoryelement related to the present invention belongs to the former type.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a semiconductormemory element of an improved construction so contrived as to suppressdiffusion of hydrogen or intrusion of water content into a capacitorhaving a ferroelectric thin film, and also to provide a method ofmanufacturing such an improved memory element.

For the purpose of achieving the object mentioned above, the capacitorstructure of the semiconductor memory element according to the presentinvention comprises: (a) a lower electrode formed on a semiconductorsubstrate; (b) a capacitor part composed of a ferroelectric thin filmformed on the lower electrode; and (c) an upper electrode formed on thecapacitor part. The capacitor structure further has: (d) a firstprotective layer consisting of one or more layers formed between thesemiconductor substrate and the lower electrode, and composed of amaterial selected from those of Group IVa transition metal, Group Vatransition metal, Group IVa transition metal nitride, Group Vatransition metal nitride, silicon nitride, nickel and palladium; and (e)a second protective layer consisting of one or more layers formed on theupper electrode, and composed of a material selected from those of GroupIVa transition metal, Group Va transition metal, Group IVa transitionmetal nitride, Group Va transition metal nitride, nickel and palladium.

In the capacitor structure of the semiconductor memory element of thepresent invention, it is preferred that the upper electrode covers thecapacitor part, the lower electrode and the first protective layer viaan insulator layer. In this case, it is further preferred that thesecond protective layer covers the surface of the upper electrode. Here,the expression of covering the surface of the upper electrode with thesecond protective layer does not signify that, when the upper electrodefunctions also as a wiring (e.g. plate line), the second protectivelayer covers even such wiring as well. This definition applies to thefollowing description also.

A method of forming a capacitor structure of a semiconductor memoryelement according to a first aspect of the present invention forachieving the above object comprises the steps of: (a) forming, on asemiconductor substrate, a first protective layer consisting of one ormore layers composed of a material selected from those of Group IVatransition metal, Group Va transition metal, Group IVa transition metalnitride, Group Va transition metal nitride, silicon nitride, nickel andpalladium; (b) forming a lower electrode layer on the first protectivelayer; (c) forming a lower electrode by patterning the lower electrodelayer and the first protective layer; (d) forming a ferroelectric thinfilm on the lower electrode, and patterning the ferroelectric thin filmto thereby form a capacitor part composed of the ferroelectric thinfilm; (e) forming an insulator layer on the entire surface, and thenforming an opening in the insulator layer at a position above thecapacitor part; (f) forming an upper electrode layer on the insulatorlayer inclusive of the opening; (g) forming a second protective layerconsisting of one or more layers formed on the upper electrode layer,and composed of a material selected from those of Group IVa transitionmetal, Group Va transition metal, Group IVa transition metal nitride,Group Va transition metal nitride, nickel and palladium; and (h) formingan upper electrode by patterning the second protective layer and theupper electrode layer.

A method of forming a capacitor structure of a semiconductor memoryelement according to a second aspect of the present invention forachieving the above object comprises the following steps instead of thesteps (f), (g) and (h) defined in the method according to the secondembodiment: (i) forming an upper electrode layer on the insulator layerinclusive of the opening, and then patterning the upper electrode layerto thereby form an upper electrode; and (j) forming, on the upperelectrode, a second protective layer consisting of one or more layersand composed of a material selected from those of Group IVa transitionmetal, Group Va transition metal, Group IVa transition metal nitride,Group Va transition metal nitride, nickel and palladium, and thenpatterning the second protective layer in such a manner that the surfaceof the upper electrode is covered with the second protective layer.

A method of forming a capacitor structure of a semiconductor memoryelement according to a third aspect of the present invention forachieving the above object comprises the following steps instead of thesteps (c) and (d) defined in the method according to the firstembodiment: (k) forming a ferroelectric thin film on the lower electrodelayer; and (l) patterning the ferroelectric thin film, the lowerelectrode layer and the first protective layer to thereby form acapacitor part composed of the ferroelectric thin film, and a lowerelectrode.

A method of forming a capacitor structure of a semiconductor memoryelement according to a fourth aspect of the present invention forachieving the above object comprises the steps of: (a) forming, on asemiconductor substrate, a first protective layer consisting of one ormore layers composed of a material selected from those of Group IVatransition metal, Group Va transition metal, Group IVa transition metalnitride, Group Va transition metal nitride, silicon nitride, nickel andpalladium; (b) forming a lower electrode layer on the first protectivelayer; (c) forming a ferroelectric thin film on the lower electrodelayer; (d) patterning the ferroelectric thin film, the lower electrodelayer and the first protective layer to thereby form a capacitorcomposed of said ferroelectric thin film, and a lower electrode; (e)forming an insulator layer on the entire surface, and then forming anopening in the insulator layer at a position above the capacitor part;(f) forming an upper electrode layer on the insulator layer inclusive ofthe opening, and then patterning the upper electrode layer to therebyform an upper electrode; and (g) forming, on the upper electrode, asecond protective layer consisting of one or more layers and composed ofa material selected from those of Group IVa transition metal, Group Vatransition metal, Group IVa transition metal nitride, Group Vatransition metal nitride, nickel and palladium, and then patterning thesecond protective layer in such a manner that the surface of the upperelectrode is covered with the second protective layer.

In the present invention, an exemplary material for composing the lowerelectrode may be Pt, RuO₂, IrO₂, La--Sr--Co--O (LSCO) having aperovskite structure, or a two-layer structure of LSCO/Pt formed in thisorder from below. Meanwhile, an exemplary material for composing theupper electrode may be Pt, RuO₂, IrO₂ or aluminum alloy.

The ferroelectric thin film may be composed of a perovskite typeferroelectric material of a Bi-series layer structure. Morespecifically, an exemplary material suited for composing theferroelectric thin film may be Bi₂ SrTa₂ O₉, Bi₂ SrNb₂ O₉,Bi₂ BaTa₂ O₉,Bi₄ SrTi₄ O₁₅, Bi₄ Ti₃ O₁₂, Bi₂ SrTaxNb_(2-x) O₉, or Bi₂ PbTa₂ O₉.Particularly it is preferred that the ferroelectric thin film becomposed of a Y1-series material (Bi₂ (Sr, Ba, Ca) (Ta, Nb)₂ O₉). And itis further preferred that the Y1-series material be composed of Bi₂SrTa₂ O₉. Other exemplary materials suited for composing theferroelectric thin film are PZT and PLZT.

The first protective layer or the second protective layer may consist ofa single layer of a material selected from those of Group IVa transitionmetal (Ti, Zr, Hf), Group Va transition metal (V, Nb, Ta), Group IVatransition metal nitride, Group Va transition metal nitride, siliconnitride, nickel and palladium. The first or second protective layer mayconsist of a two-layer structure which is composed of the followingmaterials deposited in the shown order from below.

Group IVa transition metal/Group Va transition metal

Group IVa transition metal/Group IV transition metal nitride

Group IVa transition metal/Group Va transition metal nitride

Group Va transition metal/Group IVa transition metal

Group Va transition metal/Group IVa transition metal nitride

Group Va transition metal/Group Va transition metal nitride

Group IVa transition metal nitride/Group IVa transition metal

Group IVa transition metal nitride/Group Va transition metal

Group IVa transition metal nitride/Group Va transition metal nitride

Group Va transition metal nitride/Group IVa transition metal

Group Va transition metal nitride/Group IVa transition metal nitride

Group Va transition metal nitride/Group Va transition metal

Further, the first or second protective layer may consist of athree-layer structure composed of the following materials for example.

Group IVa transition metal/Group IVa transition metal nitride/Group IVatransition metal

Group IVa transition metal/Group IVa transition metal nitride/Group Vatransition metal

Group IVa transition metal/Group Va transition metal nitride/Group IVatransition metal p1 Group IVa transition metal/Group Va transition metalnitride/Group Va transition metal

Group Va transition metal/Group Va transition metal nitride/Group IVatransition metal

Group Va transition metal/Group Va transition metal nitride/Group Vatransition metal

In the above examples of multilayer compositions, any transition metalor transition metal nitride may be replaced with silicon nitride, nickelor palladium.

The semiconductor substrate may be composed of any of known insulatormaterials such as SiO₂, BPSG, PSG, BSG, AsSG, PbSG, SbSG, SOG, SiON,SiN, NSG and LTO; or an intermediate insulator layer composed bylaminating such insulator materials. The substrate may also be anelement isolating region having a LOCOS structure or a trench structure.

Similarly, the insulator layer formed under the upper electrode may becomposed of any of known insulator materials such as SiO₂, BPSG, PSG,BSG, AsSG, PbSG, SbSG, SOG, SiON, SiN, NSG and LTO; or an intermediateinsulator layer composed by laminating such insulator materials.

The structure of the semiconductor memory element according to thepresent invention can be embodied in an example where one of thesource-drain regions and the upper electrode of the selective transistorconstituting the semiconductor memory element are connected electricallyto each other via a contact plug and a wiring, while the lower electrodeis connected to a plate line; or in another example where one of thesource-drain regions and the lower electrode of the selective transistorare connected electrically to each other via a contact plug, while theupper electrode is connected to a plate line. The former example isgenerally termed a planar semiconductor memory element, and the latterexample is generally termed a stacked semiconductor memory element. Inthe stacked semiconductor memory element where one of the source-drainregions and the lower electrode of the selective transistor are mutuallyconnected via the first protective layer, it is desired that theelectric conductivity of the first protective layer be less than 0.01Ωcm or so. In this case, therefore, using silicon nitride for the firstprotective layer is not considered to be adequate.

In the present invention, the capacitor structure of the semiconductormemory element is surrounded with the first and second protectivelayers. And Group IVa transition metal or Group Va transition metal hasproperties to occlude hydrogen. Meanwhile Group IVa transition metalnitride, Group Va transition metal nitride, silicon nitride, nickel orpalladium has properties to effectively prevent diffusion of hydrogen.In this case, the first and second protective layers composed of suchmaterials have a barrier effect against intrusion of water content.Therefore, the provision of the first and second protective layersrealizes effective suppression of diffusion and intrusion of hydrogen orwater content into the capacitor structure at the time of executing ahydrogen or heat treatment. As a result, there occurs no deteriorationof the polarization characteristic of the capacitor structure, henceenhancing the long-term reliability of the semiconductor memory element.Moreover, when the substrate is composed principally of SiO₂, Group IVatransition metal or Group Va transition metal exerts a function ofenhancing the adhesion between the lower electrode and the substrate.

The above and other features and advantages of the present inventionwill become apparent from the following description which will be givenwith reference to the illustrative accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a typical partially sectional view of a ferroelectriccapacitor;

FIG. 2 graphically shows a hysteresis loop obtained in residualpolarization of a ferroelectric by impression of an external electricfield thereto;

FIG. 3 is a typical sectional view of a nonvolatile memory cell using aferroelectric capacitor;

FIG. 4 is a typical partially sectional view of a nonvolatile memorycell using a ferroelectric capacitor according to Embodiment 1;

FIG. 5 is an equivalent circuit diagram of the nonvolatile memory cellshown in FIG. 4;

FIGS. 6A to 6F are sectional views of a memory cell for explaining stepsin manufacture of a semiconductor memory in Embodiment 1;

FIGS. 7A to 7C are sectional views of a memory cell for explaining stepsin manufacture of a semiconductor memory in Embodiment 2;

FIGS. 8A to 8E are sectional views of a memory cell for explaining stepsin manufacture of a semiconductor memory in Embodiment 3; and

FIGS. 9A to 9D are sectional views of a memory cell for explaining stepsin manufacture of a semiconductor memory in Embodiment 4.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As shown in a typical partially sectional view of FIG. 1, an exemplaryferroelectric capacitor, which is used in a nonvolatile memory cellhaving a structure of one capacitor plus one transistor (selectivetransistor) where a selective transistor is additionally connected tothe ferroelectric capacitor, consists of an insulator layer 101, a lowerelectrode 102 and an upper electrode 103 formed thereon, and aferroelectric thin film 104 interposed between such two electrodes. In anonvolatile memory cell of this type, an operation of writing or readingdata is performed by applying the P-E hysteresis loop of theferroelectric shown graphically in FIG. 2. When an external electricfield being impressed to the ferroelectric thin film is removedtherefrom, the ferroelectric thin film represents spontaneouspolarization. And the residual polarization of the ferroelectric thinfilm becomes +Pr in accordance with impression of a positive externalelectric field or becomes -Pr in accordance with impression of anegative external electric field. It is supposed here that "0" signifiesone state +Pr (corresponding to D in FIG. 2) of the residualpolarization, and "1" signifies the other state -Pr (corresponding to Ain FIG. 2) of the residual polarization.

In order to discriminate between the states of "1" and "0", a positiveexternal electric field for example is impressed to the ferroelectricthin film. Then the polarization of the ferroelectric thin film isturned to the state C in FIG. 2. In this case, if the data is "0", thepolarization of the ferroelectric thin film is changed from D to C.Meanwhile, if the data is "1", the polarization of the ferroelectricthin film is changed from A via B to C. Thus, when the data is "0",there occurs none of polarization inversion in the ferroelectric thinfilm. However, when the data is "1", polarization inversion is caused inthe ferroelectric thin film. As a result, a difference is produced inthe stored charge amount in the ferroelectric capacitor. This storedcharge is detected as a signal current by turning on the selectivetransistor of the selected memory cell. If the external electric fieldis reduced to zero after reading the data, the polarization of theferroelectric thin film is turned to the state D in FIG. 2 regardless ofwhether the data is "0" or "1". Therefore, when the data is "1", anegative external field is impressed to turn the polarization to thestate A via D and E, whereby the data "1" is written.

In a ferroelectric thin film composed of a perovskite ferroelectricmaterial of Bi-series layer structure (hereinafter referred to asbismuth layer ferroelectric thin film in some cases), there is notobserved a fatigue phenomenon (deterioration of the residualpolarization caused by repeated rewriting of data) which is the worstdefect in the known PZT-series ferroelectric thin film, so that it iscurrently attracting attention as a ferroelectric thin film suited foruse in the aforementioned nonvolatile memory.

However, in the capacitor structure composed of such a bismuth layerferroelectric thin film, there arises a problem of improper operationdue to deterioration of the polarization characteristic (reduction ofthe residual polarization ±Pr) derived from the process of manufacturingthe semiconductor memory element. The present inventors have found thatthe cause of the above problem resides in intrusion of hydrogen or waterinto the ferroelectric thin film. For example, in a bismuth layerferroelectric thin film which is composed of a Y1-series material (suchas Bi₂ SrTa₂ O₉) which is represented by (Bi₂ (Sr, Ba, Ca) (Ta, Nb)₂O₉), there essentially occurs almost no deterioration of the residualpolarization ±Pr. Nevertheless, if hydrogen is diffused into such aY1-series material, deterioration of the residual polarization ±Pr ispractically induced. It has been found that, if the capacitor structureshown in FIG. 1 is treated with hydrogen under exemplary conditions of a100% hydrogen atmosphere and a treatment temperature of 420° C., thevalue of Pr+|-Pr| is lowered approximately by 20% in comparison with thevalue prior to the hydrogen treatment.

In the process of manufacturing a semiconductor memory element, ahydrogen treatment is executed to eliminate a dangling bond which isexistent, for example, in the interface between a silicon semiconductorsubstrate and a silicon oxide film. Therefore, in manufacture of anysemiconductor memory element having a capacitor structure composed of aferroelectric thin film, it is necessary to prevent impairment of thereliability of the ferroelectric thin film that may be caused byintrusion of hydrogen into the ferroelectric thin film. Meanwhile, it isalso necessary on the other hand to diffuse hydrogen into the selectivetransistor of the semiconductor memory element. In the related art knownheretofore, there is adopted a step of inhibiting diffusion of hydrogeninto the capacitor structure inclusive of the selective transistor, byeliminating execution of a hydrogen treatment (e.g., in an atmospherecontaining H₂ of 3 to 100% and at 400 to 450° C.) before or afterforming a wiring of aluminum alloy or the like, or by not forming ahydrogen-containing thin film (e.g., SiHN film produced by plasma CVD,or SiHN film produced by optical CVD), or by forming ahydrogen-containing thin film at a low temperature of 200 to 350° C. andthereafter not executing a heat treatment at any higher temperature(e.g., 350 to 450° C.). According to the above step, however, thecharacteristic of the selective transistor is deteriorated. And whenvarious heat treatments are executed during the process of manufacturingthe semiconductor memory element, the water content left in theinsulator layer and so forth intrudes into the capacitor structure toconsequently induce a phenomenon of lowering the residual polarization±Pr.

As a semiconductor memory element contrived for the purpose ofpreventing diffusion of oxygen, there is known an example having such astructure as shown in a typical partially sectional view of FIG. 3 anddisclosed in a cited reference: "A Half-Micron Ferroelectric Memory CellTechnology with Stacked Capacitor Structure", S. Onishi, et al., IEDM94pp. 843-846. In this semiconductor memory element, a source region 83, agate electrode 84 and a drain region 85 are formed in areas of asemiconductor substrate 81 divided by an element isolating region 82,and a bit line 86 is connected to the drain region 85 via a contactopening formed in an upper intermediate insulator layer 112 and a lowerintermediate insulator layer 106. The source region 83 is connected to aground layer 107 via a contact plug 87, and the ground layer 107, whichis composed of a Ti layer and a TiN layer formed in this order frombelow, is provided between a lower electrode 105 of platinum (Pt) andthe lower intermediate insulator layer 106. The ground layer 107composed of such Ti layer and TiN layer is provided in an attempt toprevent diffusion into the lower electrode 105 of platinum and also toenhance the adhesion to the lower intermediate insulator layer 106. Thelower electrode 105 and a ferroelectric thin film 108 are formed on theground layer 107. And further a TiO₂ layer 109 is formed on the lowerintermediate insulator layer 106, on the side faces of the ferroelectricthin film 108, the lower electrode 105 and the ground layer 107, andalso on a portion of the top of the ferroelectric thin film 108, in sucha manner as to cover the ferroelectric thin film 108, the lowerelectrode 105 and the ground layer 107. This TiO₂ layer 109 is providedfor preventing diffusion of oxygen. An insulator layer 110 is formed onthe TiO₂ layer 109, and an opening is formed in the TiO₂ layer 109 andthe insulator layer 110 above the ferroelectric thin film 108, andfurther an upper electrode 111 is formed on the insulator layerinclusive of such an opening. The technology disclosed in this citedreference is concerned with prevention of diffusion of oxygen into thecapacitor structure, but is not concerned with prevention of diffusionof hydrogen into the capacitor structure, particularly into theferroelectric thin film 108. Moreover, the TiO₂ layer 109 is not capableof effectively preventing diffusion of hydrogen, since the TiO₂ layer109 covers merely the side face of the capacitor and a portion of itstop, and it is considered impossible to prevent diffusion of hydrogenvia the upper platinum electrode 111 which is not covered completelywith the TiO₂ layer 109. And it is presumed that the effect attainableby the use of TiO₂ for preventing diffusion of hydrogen is inferior tothe effect attained by the use of Ti or TiN.

(Embodiment 1)

Embodiment 1 relates to a capacitor structure of a semiconductor memoryelement in the present invention, and also to a method of forming thecapacitor structure of the semiconductor memory element according to thefirst aspect of the invention. A ferroelectric thin film is composed ofa Y1-series material of Bi₂ SrTa₂ O₉, and each of a first protectivelayer 21 and a second protective layer 27 has a two-layer structurewhich consists of a layer of Group IVa transition metal and anotherlayer of Group IVa transition metal nitride. More specifically, each ofthe first protective layer 21 and the second protective layer 27 has atwo-layer structure consisting of a Ti layer and a TiN layer in thisorder from below. The semiconductor memory element consists of theaforementioned nonvolatile memory cell (known as FERAM). In thesemiconductor memory cell represented by Embodiment 1, one ofsource-drain regions 14 and an upper electrode 26 of a selectivetransistor are connected electrically to each other via a contact plug34 and a wiring 32, while a lower electrode 22 is connected to a plateline. And this element has a construction of so-called planarsemiconductor memory element where the capacitor structure is not formedabove the selective transistor 38. Now, Embodiment 1 will be describedbelow with reference to FIGS. 4, 5 and 6A-6F.

FIG. 4 is a typical partially sectional view showing the semiconductormemory element of Embodiment 1. And an equivalent circuit of thesemiconductor memory element is shown in FIG. 5. The selectivetransistor constituting the semiconductor memory element consists ofsource-drain regions 14 and a channel region 15 formed on a siliconsemiconductor substrate 10, a gate electrode 13 formed above the channelregion 15, an element isolating region 11 having a LOCOS structure, anda gate oxide film 12 formed under the gate electrode 13. The gateelectrode 13 serves also as a word line and is composed of, e.g.,polysilicon, polycide or metal silicide. The source-drain regions 14 andthe gate electrode 13 are covered with an intermediate insulator layer20. This intermediate insulator layer 20 corresponds to a substrate andis composed of BPSG for example.

A capacitor structure is formed on the intermediate insulator layer 20on the element isolating region 11. The capacitor structure consists ofa lower electrode 22 of platinum (Pt), a ferroelectric thin film 23, andan upper electrode 26 of platinum. The lower electrode 22 is formed onthe intermediate insulator layer 20 corresponding to a substrate. Theferroelectric thin film 23 is formed on the lower electrode 22. And theupper electrode 26 is formed on the ferroelectric thin film 23 via anopening 25.

A first protective layer 21 is formed between the intermediate insulatorlayer 20 corresponding to a substrate and the lower electrode 22.Meanwhile a second protective layer 27 is formed on the upper electrode26. In Embodiment 1, each of the first protective layer 21 and thesecond protective layer 27 has a two-layer structure consisting of alayer of Group IVa transition metal (concretely Ti) and a layer of GroupIVa transition metal nitride (concretely TiN). In this structure, thelayer composed of Ti is a lower one, while the layer composed of TiN isan upper one. In FIG. 4, the first protective layer 21 and the secondprotective layer 27 are illustrated as a single layer. In Embodiment 1,the upper electrode 26 covers the ferroelectric thin film 23, the lowerelectrode 22 and the first protective layer 21 via an insulator layer 24composed of SiO₂ for example.

An upper insulator layer 30 composed of BPSG for example is formed onthe second protective layer 27. The upper electrode 26 is connected viathe second protective layer 27 to a wiring 32 which extends in anopening 31 formed in the upper insulator layer 30. Further the wiring 32is connected to one of the source-drain regions 14 (e.g., source region)of the selective transistor via a contact plug 34 provided in the upperinsulator layer 30 and the intermediate insulator layer 20. Meanwhilethe other of the source-drain regions 14 (e.g., drain region) of theselective transistor is connected to a bit line 37 via a contact plug 36provided in the upper insulator layer 30 and the intermediate insulatorlayer 20. The lower electrode 22 is connected to a plate line, but suchconnection is omitted in the illustration.

Now a method of manufacturing a planar semiconductor memory element inEmbodiment 1 will be described below with reference to FIGS. 6A to 6Fwhich are typical partially sectional views of a semiconductor substrateand so forth.

[Step 1]

First, an element isolating region 11 having a LOCOS structure is formedon a silicon semiconductor substrate 10 by a known method. Subsequentlythe surface of the semiconductor substrate 10 is oxidized to form a gateoxide film 12. Then a polysilicon layer is deposited on the entiresurface by a process of CVD for example, and thereafter the polysiliconlayer is patterned by photolithography and etching to form a gateelectrode 13 composed of polysilicon. This gate electrode 13 serves alsoas a word line. Next, impurity ions are implanted and then the implantedimpurity is activated to thereby form source-drain regions 14 and achannel region 15. Thus, a selective transistor in the semiconductormemory element is formed.

The element isolating region 11 having a LOCOS structure may be replacedwith one having a trench structure. And the gate electrode 13 composedof a polysilicon layer may be replaced with one composed of polycide ormetal silicide.

[Step 2]

Subsequently an intermediate insulator layer 20 corresponding to asubstrate is formed on the semiconductor substrate 10 by a process ofCVD for example. In this manner, there is produced the structure shownin FIG. 6A. It is preferred that, after the intermediate insulator layer20 composed of BPSG is formed, this layer 20 be caused to reflow for atime of, e.g., 20 minutes at 900° C. in an atmosphere of nitrogen gas.It is further preferred that, when necessary, the top surface of theintermediate insulator layer 20 be polished and flattened chemically andmechanically by a process of chemical mechanical polishing (CMP), or beflattened by a process of resist etch back. The exemplary film formingconditions relative to the intermediate insulator layer 20 are asfollows.

    ______________________________________                                        Gas used:           SiH.sub.4 /PH.sub.3 /B.sub.2 H.sub.6                      Film forming temperature:                                                                         400° C.                                            Reaction pressure:  Atmospheric pressure                                      ______________________________________                                    

[Step 3]

Thereafter a first protective layer 21 is formed on the intermediateinsulator layer 20 corresponding to a substrate. In Embodiment 1, thefirst protective layer 21 has a two-layer structure consisting of a Tilayer and a TiN layer in this order from below. The Ti layer and the TiNlayer are obtained by sputtering under the film forming conditions givenbelow. The first protective layer 21 has a function of preventingdiffusion of hydrogen and intrusion of water content into a capacitorstructure which will be formed later. Further, the Ti layer has also afunction of enhancing the adhesion between the substrate and a lowerelectrode which will be formed next.

    ______________________________________                                        Ti layer (Thickness: 20 nm)                                                   Process gas:         Ar = 35 sccm                                             Pressure:            0.20 Pa (1.5 mTorr)                                      DC power:            400 W                                                    Film forming temperature:                                                                          Room temperature                                         TiN layer (Thickness: 100 nm)                                                 Process gas:         N.sub.2 /Ar = 100/35 sccm                                Pressure:            0.40 Pa (3.0 mTorr)                                      DC power:            900 W                                                    Film forming temperature:                                                                          Room temperature                                         ______________________________________                                    

[Step 4]

Subsequently a lower electrode layer is formed on the first protectivelayer 21. More specifically, a lower electrode layer composed ofplatinum (Pt) is deposited by DC sputtering on the entire surfaceinclusive of the top of the first protective layer 21. The thickness ofthe lower electrode layer is set to 0.1-0.2 μm. Exemplary DC sputteringconditions are as follows.

    ______________________________________                                        DC power:            200 W                                                    Process gas:         Ar = 40 sccm                                             Pressure:            0.20 Pa (1.5 mTorr)                                      Film forming temperature:                                                                          Room temperature                                         Deposition rate:     10 mm/minute                                             ______________________________________                                    

It is also possible to adopt a process of pulse laser deposition forforming the lower electrode layer of platinum (Pt). Exemplaryplatinum-film forming conditions by pulse laser deposition are asfollows.

    ______________________________________                                        Film forming conditions by pulse laser deposition:                            ______________________________________                                        Target:        Pt                                                             Laser used:    KrF excimer laser (Wavelength 248 nm,                                         Pulse width 25 nsec, 5 Hz, 1.1 J/cm.sup.2)                     Film forming temperature:                                                                    500-600° C.                                             ______________________________________                                    

The lower electrode layer can also be composed of LSCO and Pt in thisorder from below. Exemplary LSCO-film forming conditions by a process ofpulse laser ablation are as follows.

    ______________________________________                                        Target:        LSCO                                                           Laser used:    KrF excimer laser (Wavelength 248 nm,                                         Pulse width 25 nsec, 3 Hz)                                     Output energy: 400 mJ (1.1 J/cm.sup.2)                                        Film forming temperature:                                                                    550-600° C.                                             Oxygen partial pressure:                                                                     40-120 Pa                                                      ______________________________________                                    

[step 5]

Thereafter the lower electrode layer and the first protective layer arepatterned by the art of ion milling for example to form a lowerelectrode 22 from the lower electrode layer. Thus, the structure showntypically in FIG. 6B can be obtained. Although the lower electrode 22serves also as a plate line, this state is omitted in the illustration.

[Step 6]

Next a ferroelectric thin film is formed on the lower electrode 22, andthen the ferroelectric thin film is patterned to thereby form acapacitor part 23 which is composed of the ferroelectric thin film (FIG.6C). More specifically, a ferroelectric thin film composed of aperovskite ferroelectric material of a Bi-series layer structure isfirst formed on the entire surface by a process of MOCVD. Exemplary filmforming conditions relative to a Y1-series material of Bi₂ SrTa₂ O₉ areas follows.

    ______________________________________                                        Source material:   Bi(C.sub.6 H.sub.5).sub.3                                                     Sr(C.sub.11 H.sub.19 O.sub.2).sub.2                                           Ta(OC.sub.2 H.sub.5).sub.5                                 Film forming temperature:                                                                        550-750° C.                                         Film forming pressure:                                                                           1.3 × 10-1.3 × 10.sup.3  Pa                                       (0.1-1 Torr)                                               Oxygen density:    50%                                                        ______________________________________                                    

The ferroelectric thin film may be composed of Bi₂ SrTa₂ O₉ and formedby a process of pulse laser ablation. Exemplary film forming conditionsfor producing a ferroelectric thin film of Bi₂ SrTa₂ O₉ are given below.It is desired that the film of Bi₂ SrTa₂ O₉ formed under such conditionsbe treated by post-baking in an oxygen atmosphere for one hour at 800°C.

    ______________________________________                                        Target:        Bi.sub.2 SrTa.sub.2 O.sub.9                                    Laser used:    KrF excimer laser (Wavelength 248 nm,                                         Pulse width 25 nsec, 5 Hz)                                     Film forming temperature:                                                                    500° C.                                                 Oxygen partial pressure:                                                                     3 Pa                                                           ______________________________________                                    

Further the ferroelectric thin film may be composed of PZT and formed bya process of magnetron sputtering. Exemplary film forming conditions aregiven below. If the target is replaced with PLZT, it becomes possible toform a ferroelectric thin film of PLZT on the entire surface.

    ______________________________________                                        Target:          PZT                                                          Process gas:     Ar/O.sub.2  = 90% by volume/10% by                                            volume                                                       Pressure:        4 Pa                                                         Power:           50 W                                                         Film forming temperature:                                                                      500° C.                                               Thickness of ferroelectric thin film:                                                          0.1-0.3 μm                                                ______________________________________                                    

It is also possible to form a ferroelectric thin film of PZT or PLZT bya process of pulse laser ablation. Exemplary film forming conditions inthis case are as follows.

    ______________________________________                                        Target:        PZT or PLZT                                                    Laser used:    KrF excimer laser (Wavelength 248 nm,                                         Pulse width 25 nsec, 3 Hz)                                     Output energy: 400 mJ (1.1 J/cm.sup.2)                                        Film forming temperature:                                                                    550-600° C.                                             Oxygen partial pressure:                                                                     40-120 Pa                                                      ______________________________________                                    

Subsequently the ferroelectric thin film layer is patterned by a processof RIE to form a ferroelectric thin film 23 composed of such layer.

[Step 7]

Next an insulator layer 24 composed of, e.g., SiO₂ is formed on theentire surface by CVD for example, and then an opening 25 is formed inthe insulator layer 24 on the ferroelectric thin film 23 by RIE (FIG.6D).

[Step 8]

Thereafter an upper electrode layer is formed on the insulator layer 24inclusive of the opening 25. The upper electrode layer of platinum forexample can be formed in the same manner as in [Step 4].

[Step 9]

Next a second protective layer 27 having a two-layer structure is formedon the upper electrode layer. In Embodiment 1, the two-layer structureof the second protective layer 27 consists of a Ti layer and a TiN layerin this order from below. The film forming conditions relative to the Tilayer and the TiN layer obtained by a process of sputtering may be thesame as those in [Step 3]. Such second protective layer 27 has afunction of preventing diffusion of hydrogen and intrusion of watercontent into the capacitor structure.

[Step 10]

Subsequently the second protective layer 27 and the upper electrodelayer are patterned by an art of ion milling for example to form anupper electrode 26 (FIG. 6E). Thus, there is obtained a structure wherethe upper electrode 26 covers the ferroelectric thin film 23, the lowerelectrode 22 and the first protective layer 21 via the insulator layer24. In Embodiment 1, the side wall of the upper electrode 26 is notcovered with the second protective layer 27 since the second protectivelayer 27 and the upper electrode layer are patterned simultaneously.However, even in this structure, there arises no problem in preventingdiffusion of hydrogen and intrusion of water content into theferroelectric thin film 23.

[step 11]

Then an upper insulator layer 30 composed of BPSG for example is formedon the entire surface. The upper insulator layer 30 may be formed in thesame manner as in [Step 2]. Subsequently an opening 31 is formed in theupper insulator layer 30 above the second protective layer 27, andopenings 33 and 35 are formed by RIE in the upper insulator layer 30 andthe intermediate insulator layer 20 above the source-drain regions 14 ofthe selective transistor. Next, in the same manner as in [Step 3], a Tilayer and a TiN layer (not shown) are formed by sputtering in this orderfrom below on the upper insulator layer 30 inclusive of the openings 31,33 and 35. Differing from the first and second protective layers 21 and27, the purposes of these Ti and TiN layers do not reside in preventingdiffusion of hydrogen or intrusion of water content into the capacitorpart 23. The TiN layer is provided for preventing damage of the siliconsemiconductor substrate 10 that may otherwise be caused by alloy spikeon the silicon semiconductor substrate 10 at the bottoms of the openings33 and 35 due to a wiring material layer of aluminum alloy to be formednext, and further for enhancing the wettability of the wiring materiallayer of aluminum alloy. Meanwhile the Ti layer is provided forobtaining an ohmic low contact resistance between the wiring materiallayer and the source-drain regions 14 at the bottoms of the openings 33and 35.

Thereafter a wiring material layer is formed by a process of hightemperature aluminum sputtering, so that the openings 31, 33 and 35 arefilled with aluminum alloy to thereby form contact plugs 34 and 36.Exemplary film forming conditions relative to the wiring material layerof aluminum alloy are as follows. Wiring material layer of aluminumalloy (Al--Cu)

    ______________________________________                                        Process gas:          Ar = 100 sccm                                           Pressure:             0.26 Pa                                                 RF power:             15 kW                                                   Substrate heating temperature:                                                                      475° C.                                          ______________________________________                                    

The high temperature aluminum sputtering adopted for forming a film ofthe wiring material layer of aluminum alloy may be replaced with anotherprocess of high temperature reflow or high pressure reflow as well. Inthe high temperature reflow, a wiring material layer of aluminum alloyis deposited on the upper insulator layer 30 under the followingexemplary conditions.

    ______________________________________                                        Process gas:          Ar = 100 sccm                                           DC power:             20 kW                                                   Sputtering pressure:  0.4 Pa                                                  Substrate heating temperature:                                                                      150° C.                                          ______________________________________                                    

Subsequently the semiconductor substrate 10 is heated up to 500° C. orso. Then the wiring material layer of aluminum alloy deposited on theupper insulator layer 30 is rendered fluidal to be thereby caused toflow into the openings 31, 33 and 35, which are thus filled certainlywith the aluminum alloy to produce contact plugs 34 and 36. Meanwhilethe wiring material layer of aluminum alloy is left on the upperinsulator layer 30. Exemplary heating conditions are as follows.

    ______________________________________                                        Heating method:  Heating reverse side of substrate                                             with gas                                                     Heating temperature:                                                                           500° C.                                               Heating time:    2 minutes                                                    Process gas:     Ar = 100 sccm                                                Process gas pressure:                                                                          1.1 × 10.sup.3  Pa                                     ______________________________________                                    

The above heating is executed by first heating a heater block, which isdisposed on the reverse side of the semiconductor substrate 10, up to apredetermined temperature (heating temperature), and then introducing aprocess gas into a space between the heater block and the semiconductorsubstrate 10 to thereby heat the semiconductor substrate 10. Thisheating method may be replaced with a lamp heating method or the like.

A process of high pressure reflow may be adopted instead of the hightemperature reflow mentioned above. In this case, a reflow is executedunder the following exemplary conditions.

    ______________________________________                                        Substrate heating temperature:                                                                       400° C.                                         Heating time:          2 minutes                                              Heating atmosphere:    Argon gas                                              Atmosphere pressure:   Over 10.sup.6  Pa                                      ______________________________________                                    

Finally a wiring 32 and a bit line 37 are formed by patterning thewiring material layer of aluminum alloy, the TiN layer and the Ti layeron the upper insulator layer (FIG. 4).

(Embodiment 2)

Embodiment 2 relates to a method of forming the capacitor structure ofthe semiconductor memory element according to the second aspect of thepresent invention. More specifically, Embodiment 2 is different fromEmbodiment 1 in the procedure for forming an upper electrode and asecond protective layer. Hereinafter the method of forming the capacitorstructure of the semiconductor memory element in Embodiment 2 will bedescribed with reference to FIGS. 7A-7C.

[Step 21]

The following steps are the same as [Step 1] to [Step 7] in Embodiment1: i.e., the step of forming a first protective layer 21, which consistsof a Ti layer and a TiN layer, on an intermediate insulator layer 20corresponding to a substrate; the step of forming a lower electrodelayer on the first protective layer 21; the step of forming a lowerelectrode 22 by patterning the lower electrode layer and the firstprotective layer 21; the step of first forming a ferroelectric thin film23 on the lower electrode 22 and then patterning the ferroelectric thinfilm 23; and the step of forming an insulator layer 24 on the entiresurface and then forming an opening 25 in the insulator layer 24 on theferroelectric thin film 23. Therefore a detailed explanation on theabove steps is omitted here. The structure shown in FIG. 6D can thus beobtained.

[Step 22]

Subsequently an upper electrode layer is formed on the insulator layer24 inclusive of the opening 25, and then an upper electrode 26 is formedby patterning the upper electrode layer (FIG. 7A). Forming the upperelectrode layer can be executed in the same manner as in [Step 4]. Andpatterning the upper electrode layer can be performed by an art of ionmilling for example.

[Step 23]

Thereafter a second protective layer 27 consisting of a single layer ofGroup IVa transition metal nitride (TiN in Embodiment 2) is formed onthe upper electrode 26, and then the second protective layer 27 is sopatterned as to cover the surface of the upper electrode 26 (FIG. 7B).The film forming conditions relative to the Ti and TiN layers bysputtering may be the same as those in [Step 3]. And patterning thesecond protective layer 27 can be performed by a process of RIE forexample.

[Step 24]

Next, there are formed a wiring 32, a bit line 37 and contact plugs 34and 36 in the same manner as in [Step 11] of Embodiment 1, henceproducing the structure of FIG. 7C which is a typical partiallysectional view thereof.

In Embodiment 2, the upper electrode layer and the the second protectivelayer are patterned in mutually different steps. As a result, the upperelectrode 26 covers the ferroelectric thin film 23, the lower electrode22 and the first protective layer 21 via the insulator layer 24, andfurther the second protective layer 27 covers the surface (including theside face) of the upper electrode 26, whereby it is rendered possible toprevent diffusion of hydrogen and intrusion of water content into theferroelectric thin film with enhanced certainty.

(Embodiment 3)

Embodiment 3 relates to a method of forming the capacitor structure ofthe semiconductor memory element according to the third aspect of thepresent invention. More specifically, Embodiment 3 is different fromEmbodiment 1 in the procedure for forming a first protective layer, alower electrode and a capacitor part.

Similarly to Embodiment 1, a ferroelectric thin film 23 is composed of aY1-series material of Bi₂ SrTa₂ O₉, and each of a first protective layerand a second protective layer has a two-layer structure consisting of aGroup IVa transition metal layer and a Group IVa transition metalnitride layer as in Embodiment 1. More specifically, each of the firstand second protective layers has a two-layer structure consisting of aTi layer and a TiN layer in this order from below. The semiconductormemory element consists of the aforementioned nonvolatile memory cell(known as FERAM). In the semiconductor memory element of Embodiment 3,one of source-drain regions and a lower electrode of a selectivetransistor are connected mutually via a contact plug, while an upperelectrode is connected to a plate line. And a capacitor structure isformed above the selective transistor. That is, the above semiconductormemory element has a stacked element structure. Hereinafter Embodiment 3will be described in detail with reference to FIGS. 8A-8E.

FIG. 8E is a typical partially sectional view of the semiconductormemory element in Embodiment 3. The structure of the selectivetransistor constituting the semiconductor memory element may befundamentally the same as the structure of the selective transistordescribed in Embodiment 1.

A capacitor structure is formed on an intermediate insulator layer 20over the selective transistor. This capacitor structure consists of alower electrode 22 composed of platinum (Pt) for example, aferroelectric thin film 23, and an upper electrode 26 composed ofplatinum (Pt) for example. The lower electrode 22 is formed on theintermediate insulator layer 20 corresponding to a substrate, and theferroelectric thin film 23 is formed on the lower electrode 22. Furtherthe upper electrode 26 is formed on the ferroelectric thin film 23.

A first protective layer 21 is formed between the intermediate insulatorlayer 20, which corresponds to a substrate, and the lower electrode 22.Meanwhile a second protective layer 27 is formed on the upper electrode26. In Embodiment 3 also, each of the first protective layer 21 and thesecond protective layer 27 has a two-layer structure consisting of alayer of Group IVa transition metal (concretely Ti) and a layer of GroupIVa transition metal nitride (concretely TiN). In this structure, thelayer composed of Ti is a lower one, while the layer composed of TiN isan upper one. In this diagram, the first protective layer 21 and thesecond protective layer 27 are illustrated as a single layer. InEmbodiment 3, the upper electrode 26 covers the ferroelectric thin film23, the lower electrode 22 and the first protective layer 21 via aninsulator layer 24 composed of SiO₂ for example.

An upper insulator layer 30 composed of BPSG for example is formed onthe second protective layer 27. The upper electrode 26 is connected viathe second protective layer 27 to a wiring 42 which corresponds to aplate line and extends in an opening 31 formed in the upper insulatorlayer 30. Further the lower electrode 22 is connected to one of thesource-drain regions 14 (e.g., source region) of the selectivetransistor via a contact plug 41 provided in the first protective layer21 and the intermediate insulator layer 20. Meanwhile the other of thesource-drain regions 14 (e.g., drain region) of the selective transistoris connected to a bit line 37 via a contact plug 36 provided in theupper insulator layer 30 and the intermediate insulator layer 20.

[Step 31]

First, a selective transistor in the semiconductor memory element isproduced in the same manner as in [Step 1] of Embodiment 1.

[Step 32]

Subsequently an intermediate insulator layer 20, which corresponds to asubstrate and is composed of BPSG, is formed on the semiconductorsubstrate 10 by a process of CVD for example. It is preferred that theintermediate insulator layer 20 thus formed be caused to reflow for atime of, e.g., 20 minutes at 900° C. in an atmosphere of nitrogen gas.It is further preferred that, when necessary, the top surface of theintermediate insulator layer 20 be polished and flattened chemically andmechanically by a process of chemical mechanical polishing (CMP), or beflattened by a process of resist etch back. The film forming conditionsrelative to the intermediate insulator layer 20 may be the same as thosein [Step 2] of Embodiment 1.

Thereafter an opening 40 is formed by a process of RIE in theintermediate insulator layer 20 above one of the source-drain regions 14(e.g., source region). Then a polysilicon layer is deposited by aprocess of CVD on the intermediate insulator layer 20 inclusive of theopening 40, and the polysilicon layer on the intermediate insulatorlayer 20 is removed by a process of etch back. Subsequently an impuritysuch as phosphorus is implanted into the polysilicon layer to dope thesame by ion implantation or the like, and a heat treatment is executedto activate the impurity, thereby producing a contact plug 41 where theopening 40 is filled with the doped polysilicon (FIG. 8A).

[Step 33]

Next a first protective layer 21 is formed on the intermediate insulatorlayer 20 corresponding to a substrate. The film forming conditionsrelative to the first protective layer 21 may be the same as those in[Step 3] of Embodiment 1.

[Step 34]

Subsequently a lower electrode layer is formed on the first protectivelayer 21 in the same manner as in [Step 4] of Embodiment 1.

[Step 35]

Next a ferroelectric thin film layer is formed on the lower electrodelayer in the same manner as in [Step 6]of Embodiment 1.

[Step 36]

Thereafter the ferroelectric thin film layer, the lower electrode layerand the first protective layer are patterned by a process of RIE or thelike to form a ferroelectric thin film 23 and a lower electrode 22 ofplatinum for example. Thus, the structure shown in FIG. 8B can beobtained.

[Step 37]

Then an insulator layer 24 composed of, e.g., SiO₂ is formed on theentire surface by a process of CVD for example, and thereafter anopening 25 is formed in the insulator layer 24 on the ferroelectric thinfilm 23 by a process of RIE (FIG. 8C).

[Step 38]

Subsequently, an upper electrode layer is formed on the insulator layer24 inclusive of the opening 25. Forming the upper electrode layer ofplatinum (Pt) for example may be executed in the same manner as in [Step4].

[Step 39]

Next, a second protective layer 27 having a two-layer structure isformed on the upper electrode layer. In Embodiment 3 also, the secondprotective layer 27 has a two-layer structure consisting of a Ti layerand TiN layer in this order from below. The film forming conditionsrelative to the Ti and TiN layers by sputtering may be the same as thosein [Step 3].

[Step 40]

Thereafter an upper electrode 26 is formed by patterning the secondprotective layer 27 and the upper electrode layer by an art of ionmilling for example (FIG. 8D). Thus, there is obtained a structure wherethe upper electrode 26 covers all of the ferroelectric thin film 23, thelower electrode 22 and the first protective layer 21 via the insulatorlayer 24. In Embodiment 3 also, the side wall of the upper electrode 26is not covered with the second protective layer 27 since this layer 27and the upper electrode layer are patterned simultaneously. However,even such a structure raises no problem in preventing diffusion ofhydrogen or intrusion of water content into the capacitor part 23.

[Step 41]

Subsequently an upper insulator layer 30 composed of BPSG for example isformed on the entire surface. Forming the upper insulator layer 30 maybe executed in the same manner as in [Step 2]. Thereafter an opening isformed in the upper insulator layer 30 above the second protective layer27, and another opening is formed by a process of RIE in the upperinsulator layer 30 and the intermediate insulator layer 20 above theother of source-drain regions 14 of the selective transistor. Next, inthe same manner as in [Step 11] of Embodiment 1, a Ti layer and a TiNlayer (not shown) are formed by sputtering in this order from below onthe upper insulator layer 30 inclusive of the opening, and further awiring material layer is formed thereon, whereby the opening is filledwith aluminum alloy to consequently produce a contact plug 36. Andfinally the wiring material layer of aluminum alloy, the TiN layer andthe Ti layer on the upper insulator layer are patterned to thereby forma wiring (plate line) 42 and a bit line 37 (FIG. 8E). Although the plateline in this example is formed by the use of an aluminum wiring, theplate line may be composed of platinum of the upper electrode as well.

(Embodiment 4)

Embodiment 4 relates to a method of forming the capacitor structure ofthe semiconductor memory element according to the fourth aspect of thepresent invention. More specifically, Embodiment 4 relates to acomposite capacitor structure forming method which is a combination ofthe aforesaid procedure of forming a first protective layer, a lowerelectrode and a capacitor part described in Embodiment 3, and anotheraforesaid procedure of forming an upper electrode and a secondprotective layer described in Embodiment 2. The structure of thesemiconductor memory element is planar type mentioned in Embodiment 1.Hereinafter a method of manufacturing the semiconductor memory elementin Embodiment 4 will be described in detail with reference to FIGS.9A-9D which are typical partially sectional views of a semiconductorsubstrate and so forth.

[Step 51]

First, a selective transistor in the semiconductor memory element isformed in the same manner as in [Step 1] of Embodiment 1.

[Step 52]

Next, as in [Step 2] of Embodiment 1, an intermediate insulator layer 20corresponding to a substrate is formed on a semiconductor substrate 10by a process of CVD for example.

[Step 53]

Thereafter, as in [Step 3] of Embodiment 1, a first protective layer 21is formed on the intermediate insulator layer 20 corresponding to asubstrate. The first protective layer 21 has a two-layer structureconsisting of a Ti layer and a TiN layer in this order from below.

[Step 54]

Subsequently, as in [Step 4] of Embodiment 1, a lower electrode layercomposed of platinum for example is formed on the first protective layer21.

[Step 55]

Next, as in [Step 6] of Embodiment 1, a ferroelectric thin film layer isformed on the lower electrode layer.

[Step 56]

Thereafter the ferroelectric thin film layer, the lower electrode layerand the first protective layer are patterned by a process of RIE or thelike to form a ferroelectric thin film 23 and a lower electrode 22 ofplatinum for this example. Thus, the structure shown in FIG. 9A can beproduced.

[Step 57]

Then an insulator layer 24 composed of, e.g., SiO₂ is formed on theentire surface by a process of CVD for example, and an opening 25 isformed in the insulator layer 24 on the ferroelectric thin film 23 by aprocess of RIE.

[Step 58]

Next, an upper electrode layer is formed on the insulator layer 24inclusive of the opening 25, and then an upper electrode 26 is formed bypatterning the upper electrode layer (FIG. 9B). Forming the upperelectrode layer of platinum for example may be executed in the samemanner as in [Step 4]. Meanwhile, patterning the upper electrode layermay be performed by an art of ion milling for example.

[Step 59]

Subsequently a second protective layer 27, which has a two-layerstructure consisting of a layer of Group IVa transition metal (Ti inEmbodiment 4) and a layer of Group IVa transition metal nitride (TiN inEmbodiment 2), is formed on the upper electrode 26, and the secondprotective layer 27 is so patterned as to cover the surface of the upperelectrode 26 (FIG. 9C). Film forming conditions relative to the Ti andTiN layers by sputtering may be the same as those in [Step 3]. Andpatterning the second protective layer 27 may be performed by a processof RIE for example.

[Step 60]

Then a wiring 32, a bit line 37 and contacts 34 and 36 are formed in thesame manner as in [Step 11] of Embodiment 1, whereby there is producedthe structure shown in a typical partially sectional view of FIG. 9D.

Although the present invention has been described hereinabove withreference to some embodiments thereof, it is to be understood that thepresent invention is not limited to such embodiments alone. Thestructure of the semiconductor memory element explained in connectionwith each of the embodiments is merely illustrative, and it may bechanged or modified in design as well. For example, in the semiconductormemory element having the structure shown in FIG. 4, the firstprotective layer may be formed directly on the element isolating regionin some cases. The method of forming the capacitor structure of thesemiconductor memory element explained in Embodiments 1, 2 and 4 may beapplied also to manufacture of a stacked semiconductor memory elementexplained in Embodiment 3. Similarly, the method of forming thecapacitor structure of the semiconductor memory element explained inEmbodiment 3 may be applied to manufacture of a planar semiconductormemory element as well.

In each of the above embodiments, a contact plug is produced by firstfluidizing aluminum alloy and then filling an opening with such alloy,or by the use of polysilicon. However, it is also possible to product acontact plug by a process of blanket tungsten CVD as well. In this case,an opening is first formed in the intermediate insulator layer 20 andthe upper insulator layer 30, and then a Ti layer and a TiN layer areformed by a process of sputtering in the same manner as in [Step 3]. Andthereafter a tungsten layer is deposited on the TiN layer by a processof CVD under the following exemplary conditions.

    ______________________________________                                        Gas used:        WF.sub.6 /H.sub.2 /Ar = 40/400/2250 sccm                     Pressure:        10.7 kPa                                                     Film forming temperature:                                                                      450° C.                                               ______________________________________                                    

Subsequently the tungsten layer and the TiN and Ti layers on theintermediate insulator layer 20 and the upper insulator layer 30 areremoved by etching to consequently produce a desired contact plug wherethe opening is filled with tungsten. Thereafter a wiring layer composedof aluminum alloy is formed on the upper insulator layer 30 and then ispatterned to thereby obtain lines 32, 42 and a bit line 37. Exemplaryetching conditions are as follows.

First-stage etching: For tungsten layer

Gas used: SF₆ /Ar/He=110:90:5 sccm

Pressure: 46 Pa

RF power: 275 W

Second-state etching: For TiN layer/Ti layer

Gas used: Ar/Cl₂ =75/:5 sccm

Pressure: 6.5 Pa

RF power: 250 W

Thus, a variety of changes and modifications will be apparent to thoseskilled in the art without departing from the spirit of the invention.

The scope of the invention, therefore, is to be determined solely by theappended claims.

What is claimed is:
 1. A method of manufacturing a capacitor in anonvolatile memory cell, comprising the steps of:forming an intermediateinsulator layer on a semiconductor substrate: forming, on theintermediate insulator layer, a first protective layer including firstand second lower sub-layers wherein said first lower sub-layer iscomposed of a material selected from those of Group IVa transitionmetal, Group Va transition metal, nickel and palladium, and wherein saidsecond lower sub-layer is composed of a material selected from those ofGroup IVa transition metal nitride, Group Va transition metal nitrideand silicon nitride; forming a lower electrode layer on said firstprotective layer; forming a lower electrode by patterning said lowerelectrode layer and said first protective layer; forming a ferroelectricthin film layer on said lower electrode, and patterning saidferroelectric thin film layer to thereby form a ferroelectric thin film;forming an insulator layer over said ferroelectric thin film, said lowerelectrode and said first protective layer and connected to saidintermediate insulator layer, wherein an upper opening is maintained insaid insulator layer exposing a top surface of said ferroelectric thinfilm; forming an upper electrode layer over both said top surface ofsaid ferroelectric thin film and a top surface of said insulator layer,said upper electrode layer formed of a same material as said lowerelectrode layer; forming a second protective layer over an entire uppersurface of said upper electrode layer, said second protective layerincluding a first upper sub-layer composed of a material selected fromthose of Group IVa transition metal nitride, Group Va transition metalnitride and silicon nitride, and further including a second uppersub-layer composed of a material selected from those of Group IVatransition metal, Group Va transition metal, nickel and palladium;forming an upper electrode by patterning said second protective layerand said upper electrode layer wherein outermost edges of said upperelectrode terminate and connect with said intermediate insulator layer,and wherein said second protective layer terminates and connects withsaid outermost edges of said upper electrode or with said intermediateinsulator layer; and forming an upper insulator layer over an entireupper surface of said second protective layer and connecting to saidintermediate insulator layer, and then forming an opening in said upperinsulator layer to expose a central area of said upper surface of saidsecond protective layer.
 2. A method of manufacturing a capacitor in anonvolatile memory cell, comprising the steps of:forming an intermediateinsulator layer on a semiconductor substrate; forming, on theintermediate insulator layer, a first protective layer including firstand second lower sub-layers wherein said first lower sub-layer iscomposed of a material selected from those of Group IVa transitionmetal, Group Va transition metal, nickel and palladium, and wherein saidsecond lower sub-layer is composed of a material selected from those ofGroup IVa transition metal nitride, Group Va transition metal nitrideand silicon nitride; forming a lower electrode layer on said firstprotective layer; forming a lower electrode by patterning said lowerelectrode layer and said first protective layer; forming a ferroelectricthin film layer on said lower electrode, and patterning saidferroelectric thin film layer to thereby form a ferroelectric thin film;forming an insulator layer over said ferroelectric thin film said lowerelectrode and said first protective layer and connected to saidintermediate insulator layer, wherein an upper opening is maintained insaid insulator layer exposing a top surface of said ferroelectric thinfilm; forming an upper electrode layer over both said top surface ofsaid ferroelectric thin film and a top surface of said insulator layer,said upper electrode layer formed of a same material as said lowerelectrode layer, and then patterning said upper electrode layer to forman upper electrode wherein outermost edges of said upper electrodeterminate and connect with said intermediate insulator layer; forming asecond protective layer over an entire upper surface of said upperelectrode said second protective layer including a first upper sub-layercomposed of a material selected from the group consisting of Group IVatransition metal nitride, Group Va transition metal nitride and siliconnitride, and further including a second upper sub-layer composed of amaterial selected from the Group consisting of Group IVa transitionmetal, Group Va transition metal, nickel and palladium, and thenpatterning said second protective layer wherein said second protectivelayer terminates and connects with said outermost edges of said upperelectrode or with said intermediate insulator layer; and forming anupper insulator layer over an entire upper surface of said secondprotective layer and connecting to said intermediate insulator layer,and then forming an opening in said upper insulator layer to expose acentral area of said upper surface of said second protective layer.
 3. Amethod of manufacturing a capacitor in a nonvolatile memory cell,comprising the steps of:forming an intermediate insulator layer on asemiconductor substrate, forming, on the intermediate insulator layer, afirst protective layer including first and second lower sub-layerswherein said first lower sub-layer is composed of a material selectedfrom those of Group IVa transition metal, Group Va transition metal,nickel and palladium, and wherein said second lower sub-layer iscomposed of a material selected from those of Group IVa transition metalnitride, Group Va transition metal nitride and silicon nitride; forminga lower electrode layer on said first protective layer; forming aferroelectric thin film layer on said lower electrode layer; patterningsaid ferroelectric thin film layer, said lower electrode layer and saidfirst protective layer to thereby form a ferroelectric thin film and alower electrode; forming an insulator layer over said ferroelectric thinfilm, said lower electrode and said first protective layer and connectedto said intermediate insulator layer, wherein an upper opening ismaintained in said insulator layer exposing a top surface of saidferroelectric thin film; forming an upper electrode layer over both saidtop surface of said ferroelectric thin film and a top surface of saidinsulator layer, said upper electrode layer formed of a same material assaid lower electrode layer; forming a second protective layer over anentire upper surface of said upper electrode, said second protectivelayer including a first upper sub-layer composed of a material selectedfrom the group consisting of Group IVa transition metal nitride, GroupVa transition metal nitride and silicon nitride, and further including asecond upper sub-layer composed of a material selected from the groupconsisting of Group IVa transition metal, Group Va transition metal,nickel and palladium; forming an upper electrode by patterning saidsecond protective layer and said upper electrode layer wherein outermostedges of said upper electrode terminate and connect with saidintermediate insulator layer, and wherein said second protective layerterminates and connects with said outermost edges of said upperelectrode or with said intermediate insulator layer; and forming anupper insulator layer over an entire upper surface of said secondprotective layer and connecting to said intermediate insulator layer,and then forming an opening in said upper insulator layer to expose acentral area of said upper surface of said second protective layer.
 4. Amethod of manufacturing a capacitor in a nonvolatile memory cell,comprising the steps of:forming an intermediate insulator layer on asemiconductor substrate; forming, on the intermediate insulator layer, afirst protective layer including first and second lower sub-layerswherein said first lower sub-layer is composed of a material selectedfrom those of Group IVa transition metal, Group Va transition metal,nickel and palladium, and wherein said second lower sub-layer iscomposed of a material selected from those of Group IVa transition metalnitride; Group Va transition metal nitride and silicon nitride; forminga lower electrode layer on said first protective layer; forming aferroelectric thin film layer on said lower electrode layer; patterningsaid ferroelectric thin film layer, said lower electrode layer and saidfirst protective layer to thereby form a ferroelectric thin film and alower electrode; forming an insulator layer over said ferroelectric thinfilm, said lower electrode and said first protective layer and connectedto intermediate insulator layer, wherein an upper opening is maintainedin said insulator layer exposing a top surface of said ferroelectricthin film; forming an upper electrode layer over both said top surfaceof said ferroelectric thin film and a top surface of said insulatorlayer, said upper electrode layer formed of a same material as saidlower electrode layer, and then patterning said upper electrode layer toform an upper electrode wherein outermost edges of said upper electrodeterminate and connect with said intermediate insulator layer; forming asecond protective layer over an entire upper surface of said upperelectrode, said second protective layer including a first uppersub-layer composed of a material selected from the group consisting ofGroup IVa transition metal nitride, Group Va transition metal nitrideand silicon nitride, and further including a second upper sub-layercomposed of a material selected from the group consisting of Group IVatransition metal, Group Va transition metal, nickel and palladium; andforming an upper insulator layer over an entire upper surface of saidsecond protective layer and connecting to said intermediate insulatorlayer, and then forming an opening in said upper insulator layer toexpose a central area of said upper surface of said second protectivelayer.